Triazine dyes of the anthraquinone series



United States Patent Ofl ice Patented i 121 1223 3349 0892,4-dichloro-6-aryl-1,3,5-triazine can also be used in TRIAZINE DYES 01TI IE ANTHRAQUINONE the PromSS as Starting material SERIES In this casethe dyes are produced by condensing said Mikhail Vasiljevich Kazankov,Moscow, and Valentin tfiflZiIle it W 1110165 0f 1-am1n0-4-arylam1no-Nickolaevich Ufimtsev, Krasnogorsk, U.S.S.R., asanthraquinone. signorsto Gosudarstvenny Nauchno-Issledovateljsky Some of these dyestuffs canalso be obtained in a single Institute Orgalllchesklkh Prodllktov lKrflsltelel, step by the introduction of the aromatic amine, phenolateof an alkaline metal, substituted or unsubstituted amino- No Drawmg' p1964 421,096 anthraquinone or aminoanthrapyridone directly into the 12Clalms' (CL 260 249) reaction mass Without separation of the primaryproducts This invention relates to new triazine dyestuffs of the Of thecondensation If the process is carried out y p anthraquinone sen'es h ith F l 1 the succession of the substitution of chlorine atoms of Ocyanuric chloride by said residues can be changed.

The dyes of general Formula 1 are soluble in polyethylene terephthalate(lavsan). Incorporation of dyes Y l 15 into the resln melt does notaffect adversely its spinability, K/ nor does it adversely affect thephysical or mechanical N N properties of the fiber obtained. I l |l Thedyes feature high thermal stability and withstand N prolonged retentionin molten resin at a temperature of.

285 C. where X is an alkyl substituted phenyl radical, and Y and Thedyes are light fast and display good resistance to Z are similar ordiflerent radicals selected from the group wet processing, sublimationand other tests.

Example 1 CH8 CH3 Qrn-Q-NH NH-o -Nn NHCH3 I N N CH3 =0 \C/ 0 =0 CH3 I HCH3 i CH3- I lH consisting of aryl, phenoXy-, phenylamino-, anthraquino-To 215 g. of molten phenol 15 g. of 1-amino-4-mesidinonylamino,4-arylaminoanthra-quinonyl-l-amino, arthraanthraquinone and 2.6 g. ofcyanuric chloride were added pyridonylamino residues or theirderivatives. 45 at a temperature of 100 C. The reaction mixture was Ithas been found that the proposed dyes having the stirred for five hoursat 110 C., then heated and stirred Formula 1 are suitable for masscoloration of synthetic for three hours at 150 C. The mixture was thencooled fibers, polyester fibers in particular in deep blue, gray, to 70C., diluted with 300 ml. of methyl alcohol and olive, brown and greenhues. These dyestuffs can also be stirred to complete cooling. The dyewas separated by used for the dyeing of plastics. filtration, Washedwith methyl alcohol until a colorless This invention also provides aprocess for the producfiltrat Was Obtained, and dried. tion of the newtriazine dyestutfs of the anthraquinone The yield of2,4,6-tri-(4-mesidinoanthraquinonyl-1- series which comprises thecondensation of one molecular amino)- Was 13.25 g. or 80.5% by weight.

proportion of cyanuric chloride or its derivative and 1-3 The dye waspurified by precipitation as the sulfate and molecular proportions of1-amin0-4-arylaminoanthrarecrystallization from aqueous dioxane. Meltingpoint of quinone. If one or two moles of the latter are used, the the pod ct Was a ve 300 C.

remaining chloride atoms are substituted by a phe'noxy-, 1 Analysis P1093; or an arylamino group by condensing the product obtained clllatedvz s'z s s 1 at the previous step with phenolate of an alkaline metalThe dyestufif is used for mass coloratio f 1avsan i or an aromaticamine, selected from the group consisting bright reddish-b1116- ofaniline, toluidine, mesidine, l-aminoanthraquinone, Example 2 1 amino-4- arylaminoanthraquinone, and 4- amino-N- By a process similar to thatdescribed in Example 1, methyl-1,9-anthrapyridone.2,4,6-tri-(4'-para-toluidino) anthraquinonyl 1'-amin0)- 3 4 1,3,5triazine was obtained from 1 amino 4 (para- The product is useful formass coloration of lavsan in toluidino)-anthraquinone and cyanuricchloride. olive-green.

Example 4 CH3 CH3 The product can be used for dyeing lavsan in greenish-To 300 g. of molten phenol at a temperature of 100 bllle- C. were addedg. of 1-amino-4 mesidinoanthraquinone Example 3 and 4.76 of2-phenyl-4,6-dichloro-1,3,5-triazine. The mix- N ture was agitated atthis temperature for. five hours, then gradually heated to 150 C.,stlrred for three hours more at 150 C., cooled to 80 C. and diluted wrth500 ml. 0: =0 O: :0 of methyl alcohol. On cooling, the precipitate wasseparated by filtration, washed with methyl alcohol and dried. 0 NH Theyield of 2-phenyl-4,6-di-(4'-mesidinoanthraquinonyl- Hl-amino)-l,3,5-triazine was 13.54 g. or 74.5% by weight. Melting pointof the product after recrystallization from U dioxane, was above 300 C.

Analysis (in percent).-Found: N, 11.17 and 10.88.

l, H Calculated for C H N O N, 11.32.

I The product can be used for mass coloration of lavsan in violet-blue.

Example 5 The productobtained from 1-amino-4-(para-toluidin0)- CH3anthraquinone and 2-phenyl-4,6-dichloro-l,3,5-triazine by T0 60 g. ofphenol at temperature of 100 C. were 40 a process similar to thatdescribed in Example 4, dyes added 3 g. of2-ch1oro-4,6-di-(anthraquinoyl-1-amino)- lavsan in greenish-blue.

Example 6 -NH(|3 ("J-NH 1,3,5-triazine (obtained by the condensation ofone mole To 70 g. of molten phenol at 100 C. were added 3.8 of cyanuricchloride with two moles of l-aminoangof 2 ch orO 4d1-(4'mesldmoanthraqulnonyl-1'- amino)-1,3,5-triazine (obtained by thecondensation of one mole of cyanuric chloride with two moles of 1-amin0-4-mesidinoanthraquinone in nitrobenzene at a temperature of 190 C.) and3 g. of potassium phenolate; the

thraquinone in nitrobenzene at a temperature of 190 C.) and 2 g. of1-amino-4-(para-toluidino)-anthraquinone. The mixture was graduallyheated and stirred for five hours at a tem erature of 150 C. Then thereaction o mixture was cooler i to 70 0., diluted with150 ml. of 3 washeated gradually to 150 at methyl alcohol, and cooled with stirring.The. dye was. thls tempera? for hours .Then the mixture was separated byfiltration, washed with methyl alcohol and 33 F 3 g gg g' gg 2 5 33 22:ggg z t g g gg dned' The yleld of '(para'tolmdmo)'anthraqumny1' tion,washed with methyl alcohol, and dried. The yield 1'amino).-4,6-di-(anthraquinonyl-1-amino)-1,3,5-triaof 2 henOX 4,6 4'mesidinoanthra uino zine was 3 66 gor by weight The melting point 70amino) l,3,5-ti iazine was 3.4 g. or 83.5% by of the productrecrystallized from diluted dioxane was Melting point f the productrecrystanized f a above 300 C. ture of butyl alcohol and chloroform was,above 300 C.

Analysis (in percent).Found: C, 73.66; 73.41; H, Analysis (inpercent).Found: C, 75.52; H, 5.00; N,

3.92; 3.87; N, 11.16; 11.30. Calculated for C52H31NqO6; 11.50 and 11.43.Calculated for C55H43N705: C, 75.00; C, 73.5;H,3.65;N, 11.57. H, 4.92;N, 11.10.

To 70 g. of molten phenol at a temperature of 100 C. were added 3.8 g.of 2-chloro-4,6-di(4'-mesidinoanthraquinonyl-1-amino)-1,3,5-triazine,and 3 g. of aniline. The mixture was gradually heated to 150 C., stirred2 The dye obtained by a process similar to that described in Example 7from 2-chloro-4,6-di-(4-para-toluidino)-anthraquinonyl-1'-amino)-1,3,5=triazine and aniline, colors lavsan ingreenish-blue.

Example 9 A mixture of 4 g. of 4-amino-N-rnethyl-1,9-anthrapyridone,1.34 g. of cyanuric chloride and 35 ml. of nitrobenzene was heated to atemperature of 190 C. within one hour and stirred at this temperaturefor one hour; then the reaction mixture was cooled to 70 C., and 70 ml.of methyl alcohol was added. Upon cooling, the dye was separated byfiltration, washed with methyl alcohol until the filtrate becamecolorless, and dried.

The yield of2-chloro-4,6-di-(N'methy1-1',9-anthrapyridonyl-4'-amino)-1,3,5-triazinewas 4.6 g., or 96% by Weight.

To g. of molten phenol at a temperature of 100 C. were added 1.5 g. of 2chloro-4,6-di-(N'-methyl-1',9- anthrapyridonyl-4'-amino)-1,3,5-triazineand 0.74 g. of 1- amino-4-(paratoluidino) anthraquinone. The mixture wasstirred for one hour at 110 C., then for four hours at a temperature of150 C. and next cooled to 70 C.; 50 ml. of methyl alcohol was added, andthe mixture was stirred to complete cooling. The mixture was filtered,washed with methyl alcohol until the filtrate became colorless, anddried.

The yield of 2-(4-(para-toluidino)-anthraquinonyl-1' amino) 4,6 di (N"methyl 1",9" anthrapyridonyl- 4-amino)-l,3,5-triazine was 1.84 g., or byweight. Melting point was above 350 C.

The dyestufl is useful for mass coloration of lavsan in reddish-brown.

From 2 chloro 4,6 di (N' methyl 1',9' anthrapyn'donyl 4' amino) 1,3,5triazine and 1 amino- 4-mesidinoanthraquinone by a procedure analogousto that described in Example 9, a dyestutf was obtained which can beused for mass coloration of lavsan in reddishbrown.

6 g. of 1 amino 4 (para-toluidino) anthraquinone was dissolved in ml. ofdioxane, cooled to 5 C., and at this temperature 3.4 g. of cyanuricchloride, dissolved in 60 ml. of acetone, was added dropwise. Themixture was stirred at 5 C. for 30 minutes, the pH being maintained at6-7 by adding a saturated soda solution. The product was filtered andwashed with water and acetone.

The yield of 2,4 diehloro 6 (4' (para-toluidino)-anthraquinonyl-1'-amino)-1,3,5-t1iazine was 5.76 g.

To 60 g. of molten phenol at a temperature of 100 C. were added 2.6 g.of2,4-dich-loro-6-(4-(para-toluidino)-anthraquinonyl-1-amino)-1,3,5-triazineand 2.2 g.

of potassium phenolate. The temperature was raised to 140-.150 C., themixture stirred at this temperature for five hours, cooled to 70 C., andthen 120 ml. of methyl alcohol was added. The product was separated byfiltration, Washed with methyl alcohol until the filtrate becamecolorless, and dried.

The yield of. 2,4-diphenoxy-6-(4 (para-toluidino)-anthraquinonyl-1'-amino)-1,3,5-tri-azine was 2.85 gpThis dyestulf can be used for masscoloration of l-avsan in blue. The substitution of phenolateof analkaline metal by aniline in a process similar to that described in thisexample gives 2,4 dianilino 6 (4 para-toluidino)-anthraquinonyl-l-arnino)-1,3,5-triazine. In the case of the substitutionof phenolate of an alkaline metal by two molecular proportions ofl-amino-anthraquinone or 4- amino-N-methyl-anthrapyridone the dyestulfsdescribed in Examples 3 and 9 are obtained.

Example 12 2-(4' (para toluidino) T anthraquinonyl 1 amino)- 4,6 di(anthraquinonyl a 1? amino) 1,3,5 triazine was obtained by the followingprocedure. I

Five grams of l-aminoanthraquinone was dissolved in 130 g. of moltenphenol at 100 C., then 2.07 g. of cyanuric chloride .was added, and themixture was stirred for one hour at a temperature of 110 C. Then 3.68 g.of l-amin-4-(para-toluidino)-anthraquinone was added, the temperaturewas raised to 150 C., and the mixture was stirred at this.temperaturefor five hours, then cooled to 70 C., diluted with methylalcohol (250 ml.); the product was filtered and washed with methylalcohol until the filtrate became colorless.

The yield of olive dye was 8.52 g. or 90% by weight. What We claimis: 1. A triazine dye of the formula 8: V wherein X is analkylsubstituted phenyl radical, and Y and Z are radicals selected fromthe group consisting of phenyl, phenoxy-, phenylarnino-,anthraquinonylamino, 4-arylaminoanthraqinonyl-l-amino, andanthrapyridonylamino residues. a

2. 2,4,6 tri (4 rnesidinoanthraquinonyl 1- amino) 1,3,5 triazine.

3. 2,4,6 tri (4' (para toluidino) anthraquinonyl- 1' amino) 1,3,5triazine.

.4. 2 (4' (para toluidino) ---anthraquinonyl 1- amino) 4,6 di(anthraquinonyl l amino) 1,3,5- triazine.

5. 2 phenyl 4,6 di(4' mesidinoanthraquinonyll amino) 1,3,5 triazine.

6. 2 phenyl 4,6 di(4 paratoluidino) anthraquinonyl l' amino) 1,3,5triazine.

7.2 phenoxy 4,6 di(4' mesidinoanthraquinonyl- 1' amino) 1,3,5 triazine.

8. 2 anilino 4,6 di(4 mesidinoanthraquinonyl- 1' amino) 1,3,5 triazine.

9;2 anilino 4,6 di(4' (para: toluidino) anthraquinonyl 1 amino) 1,3,5triazine.

10. 2,4 diphenoxy 6 (4 (para toluidino)- anthraquinonyl 1' 7 amino)1,3,5 triazine.

11. 2 (4' (para toluidino) anthraquinonyl 1'- amino) 4,6 di (N" methyl1",9" anthrapyridonyl 4" amino) 1,3,5 triazine.

12. 2 (4' mesidinoanthraquinonyl 1' amino)- 4,6 di (N methyl 1",9"anthraquinonyl 4"- amino) 1,3,5 triazine.

, -References Cited UNITED STATES PATENTS 1,437,783 12/1922' Steinbuchet a1 260249 1,523,308 1/1925 Steinbuch et a1. 260-249 1,994,602 3/1935Weiners 260249 WALTERA. MODANCE, Primary Examiner.

N. S. MILESTONE, Examinen;

I. M. FORD, Assistant Examiner.

1. A TRIAZINE DYE OF THE FORMULA 